Copolymerization of norbornene and functional norbornene monomers

ABSTRACT

The present invention is directed to copolymers of norbornene and functional group containing norbornene comonomers and processes for the preparation thereof. These polymers may be random, alternating or block copolymers or terpolymers, etc.

FIELD OF THE INVENTION

[0001] The present invention is directed to polymer compositions. Moreparticularly, the present invention is directed to polymer compositionsobtained by ring-opening metathesis polymerization of functionalnorbornene monomers.

BACKGROUND OF THE INVENTION

[0002] Cycloolefin polymers (e.g. norbornene-based polymers) andcopolymers have received a great deal of attention in recent years. Theyhave found application in dielectric, optical, and photolithographicapplications. In addition, the utility of these materials as engineeringthermoplastics has been explored. As such, new cyclic olefin copolymersand catalysts for the efficient preparation of cyclic olefin polymersare constantly being sought.

[0003] The addition polymer of norbornene, i.e., polynorbornene orpoly(bicyclo[2.2.1]hept-2-ene, was described in U.S. Pat. No. 2,721,189.In this patent, two types of norbornene polymers were prepared. Thefirst polymer was prepared by the addition polymerization of norbornenegiving a fully saturated cyclic olefin polymer.

[0004] The second polymer was formed by “Ring-Opening MetathesisPolymerization” (ROMP) giving an unsaturated polymer backbone.

[0005] Throughout the years, work in many academic and industrialinstitutions have led to the development of ring-opening metathesispolymerization catalysts that are tolerant of functional groups. Mostnotably, are the molybdenum and ruthenium complexes that Schrock andGrubbs have developed (U.S. Pat. No. 4,681,956; U.S. Pat. No. 4,883,851;WO 96/04289). A variety of polymers with pendant functional groups havethus been prepared by ROMP. Further processing of the unsaturatedpolymers has been attempted in order to achieve materials with betterproperties. Physical blends (WO 93/06171) and chemical modification ofthe polymer structure by hydrogenation (U.S. Pat. No. 5,115,037),photolysis (EP 904767 A2) and others (U.S. Pat. No. 5,603,985) are allexamples illustrating technologies involved in the making of ROMPpolymers.

[0006] Despite all advances in the new materials prepared by ROMP, therehowever remains a need to polymerize monomers with functional groups,such as epoxides and dioxalanes, which allow further chemical reactionsto give polymers having desired physical properties.

SUMMARY OF THE INVENTION

[0007] The present invention relates to a polymer composition having theformula:

-[A]_(s)-[B]_(T)-

[0008] wherein A is a monomer repeat unit derived from one or moremonomers selected from the group consisting of:

[0009] and B is a monomer unit derived from one or more functionalnorbornene monomers selected from the group consisting of:

[0010] wherein

[0011] R^(7a) and R^(7b) are independently selected from H, hydrocarbyl,substituted hydrocarbyl, fluoroalkyl;

[0012] R^(8a) and R^(8b) are independently selected from H, hydrocarbyl,substituted hydrocarbyl, fluoroalkyl, C(O)—R⁹;

[0013] R⁹ is hydrocarbyl or substituted hydrocarbyl;

[0014] R^(5a) and R^(5b) are each independently H, hydrocarbyl, halogen,halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatomconnected substituted hydrocarbyl;

[0015] R^(6a) and R^(6b) are each independently H, hydrocarbyl, halogen,halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatomconnected substituted hydrocarbyl;

[0016] R^(5a-b) and R^(6a-b) may be taken together to form a ring, and Sand T represent the mole fraction of the respective monomer unit and sumto one with the proviso that T>0; and k=0-3 and j=1-6.

[0017] The present invention is further a process for preparingfunctionalized polymers comprising the ring opening metathesis offunctional norbornene to form homopolymers of norbornene or copolymersof norbornene wherein at least one of the monomers is a functionalnorbornene. The copolymers may be random, alternating or blockcopolymers.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates to polymers having the formula:

-[A]_(s)- and -[B]_(T)-

[0019] wherein A is a monomer repeat unit derived from one or moremonomers selected from the group consisting of:

[0020] and B is a monomer unit derived from one or more functionalnorbornene monomers selected from the group consisting of:

[0021] wherein

[0022] R^(7a-b) is H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl;

[0023] R^(8a-b) is H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl,C(O)—R⁹ where R⁹ is hydrocarbyl or substituted hydrocarbyl;

[0024] R^(5a-b) and R^(6a-b) are each independently H, hydrocarbyl,halogen, halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatomconnected substituted hydrocarbyl;

[0025] R^(5a-b) and R^(6a-b) may be taken together to form a ring, and Sand T represent the mole fraction of the respective monomer unit and sumto one with the proviso that T>0; and k=0-3 and j=1-6.

[0026] In one embodiment of the present invention, the polymers hereindescribed are prepared by a process including a ring-opening metathesispolymerization of cyclic olefins using metal complexes containing ametal-carbon double-bond which can undergo metathesis with acarbon-carbon double bond present in the monomers. Complexes such as theSchrock-type molybdenum alkylidene or the Grubbs-type ruthenium carbenecomplexes are preferred catalysts used in this invention.

[0027] As means of an example, ring-opening metathesis polymerization ofmonomers A1 and B4 is illustrated to give a polymer I, where neither thestereochemistry or the nature of end groups are implied by the drawing:

[0028] As used herein, the phrase “a monomer repeat unit derived fromone or more norbornene, substituted norbornene or functional norbornenemonomers” refers to the polymer product of the transition metalcatalyzed ring-opening metathesis polymerization of said monomers asdepicted by polymer I. It is understood that polymer I only depicts onecombination of A1 and B4 monomers and that many other combinations of A1and B4 are possible.

[0029] The polymers products described in this disclosure can be furtherhydrogenated to give a saturated backbone. For instance, polymerizationof monomers A1 and B4 by ring-opening metathesis polymerization producespolymer I as illustrated above. Polymer I can then be hydrogenated togive a polymer with a polyethylene cyclopentane-type structure, polymerII, where neither the stereochemistry or the nature of the end groupsare implied by the drawing:

[0030] The polymers described in this disclosure can be furtherhydrolized to give pendant hydroxy moieties. Polymerization of monomersA1 and B4 by ring-opening metathesis polymerization will, upon treatmentwith strong acids, give a polymer containing hydroxyl group. Similarly,the formation of free radicals is also possible from epoxide-containingmonomer units such as those originating from B2.

[0031] In ring-opening metathesis polymerization, one polymer chain isproduced per active site. An acyclic olefin can be used as achain-transfer agent. Addition of an acyclic olefin of formula III,shown below, allows improved control over the molecular weight of thepolymer and over the processibility of the reaction mixture as comparedto reactions that do not utilize chain transfer agents:

[0032] wherein R^(10a) and R^(10b) are hydrogen atom, hydrocarbyl, andsubstituted hydrocarbyl.

[0033] In this disclosure, symbols ordinarily used to denote elements inthe Periodic table take their ordinary meaning, unless otherwisespecified. Thus, N, O and S stand for nitrogen, oxygen and sulfur,respectively.

[0034] A “hydrocarbyl” group means a monovalent or divalent, linear,branched or cyclic group which contains only carbon and hydrogen atoms.Examples of monovalent hydrocarbyls include the following: C₁-C₂₀ alkyl;C₁-C₂₀ alkyl substituted with one or more groups selected from C₁-C₂₀alkyl, C₃-C₈ cycloalkyl, and aryl; C₃-C₈ cycloalkyl; C₃-C₈ cycloalkylsubstituted with one or more groups selected from C₁-C₂₀ alkyl, C₃-C₈cycloalkyl, and aryl; C₆-C₁₄ aryl; and C₆-C₁₄ aryl substituted with oneor more groups selected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl, and aryl;where the term “aryl” preferably denotes a phenyl, napthyl, oranthracenyl group. Examples of divalent (bridging) hydrocarbyls include:—CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, and 1,2-phenylene.

[0035] A “substituted hydrocarbyl” refers to a monovalent, divalent, ortrivalent hydrocarbyl substituted with one or more heteroatoms. Examplesof monovalent substituted hydrocarbyls include:2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl,4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl,2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl,4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl,2,6-dimethyl-4-phenylsulfonylphenyl,2,6-dimethyl-4-trifluoromethylphenyl,2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weaklycoordinated anion), 2,6-dimethyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl,2-chloronapth-1-yl, 4-methoxyphenyl, 4-nitrophenyl, 9-nitroanthr-10-yl,—CH₂OCH₃, cyano, trifluoromethyl, and fluoroalkyl. Examples of divalent(bridging) substituted hydrocarbyls include: 4-methoxy-1,2-phenylene,1-methoxymethyl-1,2-ethanediyl, 1,2-bis(benzyloxymethyl)-1,2-ethanediyl,and 1-(4-methoxyphenyl)-1,2-ethanediyl.

[0036] A “heteroatom” refers to an atom other than carbon or hydrogen.Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur,selenium, arsenic, chlorine, bromine, silicon, and fluorine.

[0037] A “heteroatom connected hydrocarbyl” refers to a group of thetype E¹⁰O(hydrocarbyl), E²⁰H(hydrocarbyl), or E²⁰(hydrocarbyl)₂, whereE¹⁰ is an atom selected from Group 16 and E²⁰ is an atom selected fromGroup 15.

[0038] A “heteroatom connected substituted hydrocarbyl” refers to agroup of the type E¹⁰(substituted hydrocarbyl), E²⁰H(substitutedhydrocarbyl), or E²⁰(substituted hydrocarbyl)₂, where E¹⁰ is an atomselected from Group 16 and E²⁰ is an atom selected from Group 15.

[0039] The term “fluoroalkyl” as used herein refers to a C₁-C₂₀ alkylgroup substituted by one or more fluorine atoms.

[0040] The term “halohydrocarbyl” as used herein refers to a C₁-C₂₀alkyl group substituted by one or more of fluorine, chlorine, bromine oriodine atoms.

[0041] The term “polymer” as used herein is meant a species comprised ofmonomer units and having a degree of polymerization (DP) of ten orhigher.

[0042] As used herein, the terms “monomer” and “olefin monomer” refer tothe olefin or the other monomer compound before it has been polymerized;the term “monomer units” refers to the moieties of a polymer thatcorrespond to the monomers after they have been polymerized.

[0043] The term “chain-transfer agent” as used herein refers to acompound capable of reacting with the growing polymer chain at themetal-carbon double bond by metathesis, thereby cleaving off the polymerchain and generating a new initiator capable of polymerizing themonomers by ring-opening metathesis polymerization.

[0044] The term “metathesis” herein used refers to the reaction betweena metal-carbon double bond and a carbon-carbon double bond, leading to anew metal-carbon double bond and a new carbon-carbon double bond throughthe formation of a metallocyclobutane intermediate.

[0045] In some cases, it is advantageous to attach the catalyst to asolid support. Examples of useful solid supports include: inorganicoxides, such as talcs, silicas, titania, silica/chromia,silica/chromialtitania, silica/alumina, zirconia, aluminum phosphategels, silanized silica, silica hydrogels, silica xerogels, silicaaerogels, montmorillonite clay and silica co-gels, as well as organicsupport materials such as polystyrene and functionalized polystyrene.(See, for example, S. B. Roscoe et al., “Polyolefin Spheres fromMetallocenes Supported on Non-Interacting Polystyrene,” 1998, Science,280, 270-273 (1998) the contents of which are incorporated herein byreference).

[0046] The present invention is explained in greater detail in thefollowing non-limiting Examples.

EXAMPLES Example 1

[0047] To a solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride (Strem Chemicals; 14.9 mg; 18.1 μmol) in 1 mLdichloromethane was added, under vigorous stirring, a solution ofnorbornene (298 mg; 3.16 mmol) and B2 (47.0 mg; 0.345 mmol) in 4 mLdichloromethane. The reaction was stirred at room temperature for 3hours and 30 min. A few drops of vinyl ethyl ether was then added. Afterseveral hours, the viscous solution was diluted by addition of 4 mLdichloromethane. The polymer was precipitated by addition to 75 mLmethanol. The mixture was filtered and the residual solid was dried invacuo to give 313 mg of polymer.

Example 2

[0048] To a solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride (Strem Chemicals; 9.7 mg; 10 μmol) in 2 mLdichloromethane was added, under vigorous stirring, a solution of B2(282 mg; 2.07 mmol) in 4 mL dichloromethane. The reaction was stirred atroom temperature for 20 hours. A few drops of vinyl ethyl ether was thenadded. After 2 hours, the polymer was precipitated by addition tomethanol. The mixture was filtered and the residual solid was dried invacuo. The solid was then redissolved in dichloromethane andreprecipitated by addition to methanol. The polymer was collected byfiltration and further dried in vacuo, yielding 231 mg. (T_(g)=77° C.;M_(n)=73.3K, M_(w)=139K relative to polystyrene)

Example 3

[0049] To a solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride (Strem Chemicals; 14.7 mg; 17.9 μmol) in 2 mLdichloromethane was added, under vigorous stirring, a solution ofnorbornene (258 mg; 2.74 mmol) and B1 (54.8 mg; 0.304 mmol) in 4 mLdichloromethane. The reaction was stirred at room temperature for 20hours. A few drops of vinyl ethyl ether was then added. After 2 hours,the polymer was precipitated by addition to methanol. The mixture wasfiltered and the residual solid was dried in vacuo. The solid was thenredissolved in dichloromethane and reprecipitated by addition tomethanol. The polymer was collected by filtration and further dried invacuo, yielding 273 mg. (T_(g)=35° C.; M_(n)=1932, M_(w)=33.5K relativeto polystyrene; 11 mol % incorporation of B1 by ¹H NMR analysis)

Example 4

[0050] To a solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride (Strem Chemicals; 7.7 mg; 8.2 μmol) in 2 mLdichloromethane was added, under vigorous stirring, a solution of B1(308 mg; 1.71 mmol) in 4 mL dichloromethane. The reaction was stirred atroom temperature for 20 hours. A few drops of vinyl ethyl ether was thenadded. After 2 hours, the polymer was precipitated by addition tomethanol. The mixture was filtered and the residual solid was dried invacuo. The solid was then redissolved in dichloromethane andreprecipitated by addition to methanol. The polymer was collected byfiltration and further dried in vacuo, yielding 239 mg. (T_(g)=163° C.;7.7 mol % incorporation of B1 by ¹H NMR analysis; M_(n)=63,000)

Example 5

[0051] To a solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride (Strem Chemicals; 22.0 mg; 26.7 μmol) in 3 mLdichloromethane was added, under vigorous stirring, a solution ofnorbornene (449 mg; 4.77 mmol) and B4 (143 mg; 0.736 mmol) in 4 mLdichloromethane. The reaction was stirred at room temperature for 3hours. A few drops of vinyl ethyl ether was then added. After severalhours, the polymer was precipitated by addition to methanol. The mixturewas filtered and the residual solid was dried in vacuo, yielding 559 mg.(T_(g)=44° C.; 12 mol % incorporation of B4 by ¹H NMR analysis;M_(n)(NMR)=30.6K)

Example 6

[0052] To a solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride (Strem Chemicals; 9.6 mg; 12 μmol) in 3 mLdichioromethane was added, under vigorous stirring, a solution of B4(461 mg; 2.37 mmol) in 4 mL dichloromethane. The reaction was stirred atroom temperature for 18 hours. A few drops of vinyl ethyl ether was thenadded. After 2 hours, the polymer was precipitated by addition tomethanol. The mixture was filtered and the residual solid was dried invacuo, yielding 444 mg.(T_(g)=86° C.;M_(n)(NMR)=47,100).

[0053] The foregoing is illustrative of the present invention, and isnot to be construed as limiting thereof. The invention is defined by thefollowing claims, with equivalents of the claims to be included therein.

We claim:
 1. A polymer composition comprising repeat units of theformula -[A]_(s)- and -[B]_(T)- wherein A is a monomer repeat unitderived from one or more monomers selected from the group consisting of:

and B is a monomer unit derived from one or more functional norbornenemonomers selected from the group consisting of:

wherein, R^(7a-b) is H, hydrocarbyl, substituted hydrocarbyl,fluoroalkyl; R^(8a-b) is H, hydrocarbyl, substituted hydrocarbyl,fluoroalkyl, C(O)—R⁹ where R⁹ is hydrocarbyl or substituted hydrocarbyl;R^(5a-b) and R^(6a-b) are each independently H, hydrocarbyl, halogen,halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatomconnected substituted hydrocarbyl; R^(5a-b) and R^(6a-b) may be takentogether to form a ring, and S and T represent the mole fraction of therespective monomer unit and sum to one with the proviso that T>0; and kis from 0 to 3 and j is from 1 to
 6. 2. The polymer compositionaccording to claim 1, wherein A is the monomer unit derived from A1. 3.The polymer composition according to claim 2, wherein B is the monomerunit derived from B1.
 4. The polymer composition according to claim 3,wherein S is O and T is
 1. 5. The polymer composition according to claim1 wherein B is the monomer unit derived from B2.
 6. The polymercomposition according to claim 1, wherein S is 0 and T is
 1. 7. Thepolymer composition according to claim 1, wherein B is the monomer unitderived from B4.
 8. The polymer composition according to claim 7,wherein S is 0 and T is
 1. 9. The polymer composition according to claim1, wherein the polymer is hydrogenated to remove unsaturation.
 10. Thepolymer composition according to claim 1, wherein the polymer ishydrolized to give pending hydroxyl moieties.
 11. The polymercomposition according to claim 1, wherein the polymer is a randomcopolymer.
 12. The polymer composition according to claim 1, wherein thepolymer is a block copolymer.
 13. A process for preparing a polymercomposition comprising repeat units of the formula: -[A]₃ and -[B]_(T)-which comprises contacting at least one monomer(s) selected from thegroup consisting of:

with one or more monomer(s) selected from the group consisting of:

wherein, R^(7a-b) is H, hydrocarbyl, substituted hydrocarbyl,fluoroalkyl; R^(8a-b) is H, hydrocarbyl, substituted hydrocarbyl,fluoroalkyl, C(O)—R⁹ where R⁹ is hydrocarbyl or substituted hydrocarbyl;R^(5a-b) and R^(6a-b) are each independently H, hydrocarbyl, halogen,halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatomconnected substituted hydrocarbyl; R^(5a-b) and R^(6a-b) may be takentogether to form a ring, and S and T represent the mole fraction of therespective monomer unit and sum to one with the proviso that T>0; and kis from 0 to 3 and j is from 1 to
 6. 14. A process as recited in claim13, wherein the monomers undergo ring-opening metathesis polymerization.15. A process as recited in claim 13, further comprising hydrogenatingthe polymer composition to remove unsaturation.
 16. A process as recitedin claim 13, further comprising hydrolyzing the polymer composition toprovide pendant hydroxyl moieties.
 17. A process as recited in claim 13,further comprising contacting said monomers with a chain transfercompound of the following formula:

wherein R^(10a) and R^(10b) are hydrogen atom, hydrocarbyl, andsubstituted hydrocarbyl.